Dye-sensitized TiO2 hybrid system with rhenium and cobalt catalysts for producing hydrogen/carbon monoxide syngas

ABSTRACT

Disclosed is a hybrid catalyst system for the production of hydrogen/carbon monoxide syngas. The hybrid catalyst system includes a dye, a rhenium (Re) catalyst, and a cobalt (Co) catalyst grafted on a semiconductor metal oxide. The hybrid catalyst system can produce syngas without the aid of external energy and enables control over the ratio of hydrogen/carbon monoxide formed. Therefore, the hybrid catalyst system can find application in various industrial fields, including chemical fuel production.

CROSS REFERENCES TO RELATED APPLICATIONS

The present application claims the benefit and priority to Korean Patent Application No. 10-2016-0172434, filed in the Korean Patent Office on Dec. 16, 2016. The entire disclosure of the application is incorporated herein by reference.

FIELD

The present invention relates to a hybrid catalyst system in which a dye, a rhenium (Re) catalyst, and a cobalt (Co) catalyst are grafted on a semiconductor metal oxide. More specifically, the present invention relates to a hybrid catalyst system for producing hydrogen/carbon monoxide syngas including a dye, a rhenium (Re) catalyst, and a cobalt (Co) catalyst grated on TiO₂.

BACKGROUND

Due to the global climate crisis brought by the continuous increase of CO₂ emission in the atmosphere (BP statistical Review of World Energy June 2016), the utilization of CO₂ as a carbon resource is an important subject in the science and industry fields. The reduction of CO₂ to utilizable C1 resources is a major research target in chemical conversions of solar energy, together with the hydrogen evolution by water reduction, to provide a strategic way responding the energy and environmental problems (I. Willner et al., J. Am. Chem. Soc., 109:6080-6, 1987). Among visible-light induced multi-electron reductions of CO₂, the two-electron reduction to CO is a kinetically favourable choice because of the relatively low reaction barrier compared to one-electron and other higher-reduction reactions (A. J. V. Underwood, Ind. Eng. Chem., 32:449-54. 1940). Moreover, CO is currently utilized as a carbon source for the production of chemicals in petroleum chemical industry, particularly for the methanol production from a mixture of CO and H₂, so-called syngas (M. E. Dry, Catal. Today, 71:227-41, 2002; I. Wender, Fuel Process. Technol., 48:189-297, 1996).

Syngas has been also known as a key feedstock for the production of synthetic bulk chemicals via the Fischer-Tropsch (F-T) processing (A. J. V. Underwood, Ind. Eng. Chem., 32:449-54. 1940). For the production of chemicals from syngas, the tailoring of H₂/CO ratio in syngas mixtures is critical, e.g. 2:1 H₂/CO for methanol production and F-T hydrocarbon syntheses (M. E. Dry, Catal. Today, 71:227-41, 2002; K. C. Waugh, Catal. Today, 15:51-75, 1992) and 1:1 H₂/CO for the production of aldehydes via hydroformylation of alkenes (M. Beller et al., J. Mol. Catal. A: Chem., 104:17-85, 1995). While the simultaneous formation of H₂ and CO is known to occur by photochemical and electrochemical reductions of CO₂ and water using Ni— (V. S. Thoi et al., J. Am. Chem. Soc., 135:14413-24, 2013), Re— (B. Kumar et al., Chem. Commun., 45:272-4, 2012), and Ru— (P. Kang et al., Energy Environ. Sci., 7:4007-12, 2014)-molecular catalysts, little has been referred to possible control of syngas compositions. Therefore, a new protocol that focuses on adjustability of H₂/CO ratio in visible-light induced syngas production should be of scientific significance.

Conventional technologies for catalytic production of syngas require the production of hydrogen and carbon monoxide through independent catalytic conversion processes and mixing of the gases through additional processes. Further, most of the production technologies are limited to the utilization of by-product gases and related processes thereof. Recent technologies for direct production of syngas using molecular catalysts are based on electrochemical methods that still need external energy.

Thus, the present inventors have earnestly and intensively conducted research to develop a method for direct production of syngas without the need for external energy and a catalytic system for producing syngas in which the ratio of gases formed can be controlled, and as a result, found that when two types of transition-metal complex catalysts, i.e. a rhenium catalyst and a cobalt catalyst, are immobilized on TiO₂ particles, the resulting catalytic system exhibits high catalytic activity, produces H₂ and CO without external energy, and enables control over the ratio of H₂/CO formed. The present invention has been accomplished based on this finding.

SUMMARY

It is an object of the present invention to provide a hybrid catalyst system in which a dye, a rhenium (Re) catalyst, and a cobalt (Co) catalyst are grafted on a semiconductor metal oxide.

The present invention provides a hybrid catalyst system for producing hydrogen/carbon monoxide syngas including a dye, a rhenium (Re) catalyst, and a cobalt (Co) catalyst grafted on a semiconductor metal oxide.

The hybrid catalyst system of the present invention can produce syngas without the aid of external energy and enables control over the ratio of gases formed. Therefore, the hybrid catalyst system of the present invention can find application in various industrial fields, including chemical fuel production.

BRIEF DESCRIPTION OF THE DRAWINGS

These and/or other aspects and advantages of the invention will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

FIG. 1 shows a dye-sensitized TiO₂ hybrid system with rhenium and cobalt catalysts (left) and dependences of H₂/CO formation on ratios of the catalysts (right);

FIG. 2 shows the structures of a group of candidates for photosensitizers, a group of candidates for photocatalysts, and sacrificial reagents that can be used in alternative embodiments of the present invention;

FIG. 3 is a schematic representation of a heterogeneous ternary photocatalytic system for syngas production;

FIG. 4 shows diffuse-reflectance spectra (up) and UV-vis absorption spectra and photoluminescence spectra (down);

FIG. 5 shows IR spectra of Re(I) complex (ReP) and TiO₂/ReP;

FIG. 6 shows XPS spectra of Co(III) molecular catalyst (CoP) and TiO₂/CoP: Co2p (a), Cl2p (b), C1s (c), P2p (d), O1s (e), and N1s (f);

FIG. 7 shows plots of CO (a) and H₂ (b) formation versus irradiation time for 10 mg Dye/TiO₂/ReP (0.05 μmol):CoP (0.05 μmol) in 3 mL of DMF/H₂O mixture solvent containing 0.1 M SED: water contents (vol %)=0% (black squares), 3% (red circles), 10% (green triangles), and 20% (blue reverse triangles), H₂/CO formation (μmol) on the variation of water contents (0-20 vol %) in DMF/H₂O mixture solvent (c);

FIG. 8 shows dependences of H₂/CO formation on molar ratios of ReP and CoP anchored on TiO₂; irradiation of 10 mg Dye/TiO₂/ReP:CoP (total 0.1 μmol) and 0.1 M SED in 3 mL DMF/H₂O mixture solvent (20 vol % water) for 20 h;

FIG. 9 shows CO and H₂ evolution rates per particle'

FIG. 10 shows the formation of CO and H₂ in a 4-cycle repetition at >400 nm for 400 min after CO₂ bubbling for 30 min in the dark (10 mg Dye (1.5 μmol)/TiO₂/ReP (0.05 μmol):CoP (0.05 μmol) in 3 mL DMF/H₂O mixture solvent (20 vol % water) containing 0.1 M SED);

FIG. 11 shows plots of CO (a) and H₂ (b) formation versus time for Dye/TiO₂/ReP:CoP with different loading ratio of catalysts (1:9 to 9:1);

FIG. 12 shows plots of produced syngas composition (H₂/CO) versus irradiation time for Dye/TiO₂/ReP:CoP prepared with different loading ratio of ReP and CoP (1:9 to 9:1);

FIG. 13 is a schematic representation of electron transfer processes in visible-light induced syngas production by a dual molecular catalytic hybrid system, involving (1) electron injection from excited-state Dye into TiO₂ as the initiation process, (2) competitive transfer of the injected electrons to the ReP and CoP catalyst sites through TiO₂, and (3) the chemical processes proceeding on the ReP site (CO₂ reduction) and on the CoP site (H₂ evolution) under supply of electrons from TiO₂. (4) shows that this photocatalytic cycle for syngas production can be closed after the recovery of Dye by the reduction of Dye^(⋅+) with SED;

FIG. 14 shows cyclic voltammograms of CoP/RePE (a) and SED (BIH) (b);

FIG. 15 shows Mott-Schottky plots (a) and flat-band potentials (E_(fb)) (b) for TiO₂ nanoparticle films on FTO electrode in the absence of water and in the presence of 3 vol %, 10 vol %, and 20 vol % water in acetonitrile containing 0.1 M TBAP;

FIG. 16 shows plots of H₂ formation versus time for Dye (1.5 μmol)/TiO₂ (10 mg)/ReP (0.05 μmol):CoP (0.05 μmol) with addition of CO (78 μL) (red circles) and without addition of CO (black squares) in CO₂-saturated DMF-H₂O mixture solvent (20 vol % water) containing 0.1 M SED.

DETAILED DESCRIPTION

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by the ordinary skilled in the art expert. In general, the nomenclature used herein is well-known and commonly used in the art.

In one aspect, the present invention is directed to a hybrid catalyst system including a dye, a rhenium (Re) catalyst, and a cobalt (Co) catalyst grafted on a semiconductor metal oxide (FIG. 1).

According to one embodiment of the present invention, the hybrid catalyst system includes a dye, a rhenium (Re) catalyst, and a cobalt (Co) catalyst grafted on TiO₂ and is used to produce hydrogen/carbon monoxide syngas from carbon dioxide and water.

In the present invention, the semiconductor metal oxide can receive electrons and transfer the electrons to the rhenium (Re) catalyst or the cobalt (Co) catalyst. The semiconductor metal oxide is preferably TiO₂. Other non-limiting examples of semiconductor metal oxides that can be used in the present invention include, but are not limited to, ZnO, CeO₂, C₃N₄, ZrO₂, SrTiO₂, Cu₂O, Cds, CdSe, and GaP.

In the present invention, the rhenium (Re) catalyst is [fac-[Re(4,4′-bis(diethoxyphosphorylmethyl)-2,2′-bipyridine)(CO)₃Cl].

In the present invention, the cobalt (Co) catalyst is [Co^(III)Cl(dimethylglyoximato)₂(pyridyl-4-phosphonic acid)].

The hybrid catalyst system of the present invention further includes a sacrificial reagent as an electron donor. The sacrificial reagent is preferably 1,3-dimethyl-2-phenyl-1,3-dihydrobenzimidazole but is not limited thereto.

It will be obvious to those skilled in the art that various dyes (photosensitizers), catalysts for carbon monoxide formation based on Ru, Re or Ir, organometallic catalysts, and catalysts for hydrogen formation other than the dye and the catalysts used in the present invention may be used in alternative embodiments of the present invention (FIG. 2).

The hybrid catalyst system of the present invention may further include water. The water content is 20% by volume or less. If the water content exceeds 20% by volume, the electron donor is made insoluble due to the poor solubility of the electron donor in water. Therefore, it is preferred to limit the maximum amount of water to 20% by volume.

The hybrid catalyst system of the present invention produces hydrogen/carbon monoxide syngas and enables control over the ratio of hydrogen/carbon monoxide formed. The molar ratio of hydrogen and carbon monoxide can be controlled from 1:2 to 15:1 by changing the ratio of the rhenium (Re) catalyst and the cobalt (Co) catalyst in the hybrid catalyst system of the present invention, resulting in the production of a wider variety of reactants that can be used in the Fischer-Tropsch reaction.

The hydrogen/carbon monoxide syngas is produced under visible light irradiation. Preferably, the visible light has a wavelength of at least 400 nm. The visible light may be natural light or artificial light.

The present invention will be explained in more detail with reference to the following examples. It will be evident to those skilled in the art that these examples are merely for illustrative purposes and are not to be construed as limiting the scope of the present invention. Therefore, the true scope of the present invention should be defined by the appended claims and their equivalents.

EXAMPLE 1 General Procedures

All reagents were purchased from Aldrich and used without further purification. All manipulations were performed under a dry nitrogen or argon atmosphere by using standard Schlenk techniques. N,N-Dimethylformamide (DMF) was distilled from calcium hydride and stored over molecular sieves. Acetonitrile (CH₃CN) was refluxed over and distilled from phosphorus pentoxide (P₂O₅) before use. The ¹H and ¹³C NMR spectra were recorded on a Varian Mercury 300 spectrometer operating at 300.1 and 75.4 MHz, respectively. The absorption and photoluminescence spectra were recorded on a Shimadzu UV-3101PC UV/Vis/NIR scanning spectrophotometer and on a VARIAN Cary Eclipse fluorescence spectrophotometer, respectively. The diffuse reflectance UV-visible absorption spectra of powder samples were recorded on a Scinco spectrophotometer S-3100. The IR spectra were taken on a Cary 660 FTIR spectrometer. Cyclic voltammetry (CV) measurements were carried out for DMF solutions of rhenium complex, cobalt complex, and Dye (1 mM) in the presence of tetrabutylammonium perchlorate (0.1 M) at room temperature using a BAS 100B electrochemical analyser equipped with a Pt working electrode, a platinum wire counter electrode, and an SCE reference. The Mott-Shottky (MS) measurements were carried out for acetonitrile solutions of the TiO₂ working electrode in the presence of tetrabutylammonium perchlorate (0.1 M) at room temperature using a CH Instruments CHI660D equipped with a platinum wire counter electrode and an SCE reference. Particle sizes were determined by a dynamic light scattering technique using a Microtrac UPA 150. Elemental analyses and high resolution tandem mass spectrometry were performed, respectively, on a Carlo Erba Instruments CHNS-O EA 1108 analyzer and on a Jeol LTD JMS-HX 110/110A at the Korean Basic Science Institute (Ochang).

EXAMPLE 2 Preparation of Hybrid TiO₂ Catalyst

Commercially available TiO₂ particles (Hombikat UV-100) were thoroughly washed with distilled water, ultrasonically treated in water, separated by centrifugation, and then dried in an oven under N₂. The specific Brunauer-Emmett-Teller (BET) surface areas were determined to be >250 m²/g. The TiO₂ particles (0.1 g) dispersed in an CH₃CN/tert-butanol solution of Dye (15 μmol) were allowed to stand overnight under stirring and then subjected to centrifugation. The collected particles were washed with the solvent and then dried in an oven under N₂. Similar procedures were applied to the deposition of ReP and CoP on the Dye-deposited TiO₂ powders.

Specifically, a TiO₂ hybrid system with an antenna and two transition-metal complex catalysts was prepared (FIG. 3). The antenna is (E)-2-cyano-3-(5′-(5″-(p-(diphenylamino)phenyl)thiophen-2″-yl)thiophen-2′-yl)-acrylic acid (Dye), catalyst 1 (ReP) is fac-[Re(4,4′-bis(diethoxyphosphorylmethyl)-2,2′-bipyridine)(CO)₃Cl], catalyst 2 (CoP) is [Co^(III)Cl(dimethylglyoximato)₂(pyridyl-4-phosphonic acid)]⁻, and the sacrificial electron donor (SED) is 1,3-dimethyl-2-phenyl-1,3-dihydrobenzimidazole. These compounds were synthesized according to the literature methods (E. G. Ha et al., Chem. Commun. 50:4462-4, 2014; F. Lakadamyali et al., Chem. Commun., 47:1695-7, 2011; K. R. Justin Thomas et al., Chem. Mater., 20:1830-40, 2008; X. Q. Zhu et al., J. Am. Chem. Soc., 130:2501-16, 2008). The hybrid catalyst was prepared by anchoring Dye, ReP, and CoP on TiO₂ particles (Hombikat) in this sequence. Successful anchoring of the components was confirmed by diffuse-reflectance spectroscopy, IR-absorption spectra, and X-ray photoelectron spectroscopy (XPS) of the treated particles (FIGS. 4 to 6). In each anchoring procedure, the supernatant separated by centrifugation of the treated dispersion was virtually transparent. Therefore, the amount of each component anchored on TiO₂ was estimated to approximately equal that fed.

EXAMPLE 3 Photocatalytic CO and H₂ Production

Suspensions of Dye/TiO₂/ReP:CoP particles (10 mg with 1.5 μmol dye and 0.1 μmol ReP:CoP) in 3 mL DMF/water (0-20 vol %) containing SED (0.1 M) were placed in a Pyrex cell (1 cm pass length; 6.0 mL total volume), bubbled with CO₂ for 30 min, and sealed with a septum. A series of samples were set on a homemade merry-go-round apparatus and then irradiated under magnetic stirring with a LED lamp (λ>400 nm, 60 W, model Fc-6051, Cree Inc.). The amounts of CO and H₂ evolved in the overhead space of the cell were determined by gas chromatography (HP6890A GC equipped with a TCD detector) using a SUPELCO Carboxen™ 1010 PLOT Fused Silica Capillary column. The apparent quantum yield ϕ (CO and H₂) for CO and H₂ production was determined for the Dye/TiO₂/ReP:CoP (5:5) suspensions, a band-pass filter (420-450 nm) was used to isolate the 436 nm light form the emission light of a high-pressure mercury lamp (1000 W, model 6171, Newport Corporation), and the incident light flux was determined by using a 0.2 M ferrioxalate actinometer solution (A. M. Braun et al., Photochemical Technology; Wiley&Sons: New York, 76-80, 1991).

EXAMPLE 4 CO and H₂ Formation on the Variation of Water Contents

The formation of CO and H₂ for a hybrid system of 0.05 μmol ReP/0.05 μmol CoP grafted on 10 mg TiO₂ in the presence of various amounts of water (0 to 20 vol %) was confirmed (FIG. 7). The maximum amount of water in DMF-water mixed solvent system is limited to 20 vol % due to the poor solubility of the electron donor in water. Experimentally, the dissolved ED began to be insoluble at 20 vol % water. The efficiency of CO formation increased to a maximum in the presence of 3% water, but decreased at higher contents of water. In contrast, while the H₂ formation was negligible in the absence of water and still very small in the presence of 3% water, the H₂ production activity dramatically increased in the presence of 10% water and still more at 20 vol % water. It was found that the H₂/CO ratio can be further controlled by changing the ratio of ReP:CoP grafted on TiO₂ while fixing the total amount at 0.1 μmol. Upon changing the anchoring ratio of CoP and ReP from 9:1 to 1:9, the H₂:CO ratio is systematically tuned from 1:2 to 15:1 (FIG. 8). The turnover frequency (TOF) and number (TON) of CO and H₂ evolution per molecular catalyst (ReP or CoP) and per TiO₂ nanoparticle were determined (Table 1 and FIG. 9). The apparent quantum yields (AQY) of CO and H₂ formation for the hybrid systems (Dye/TiO₂/ReP:CoP (1:9 to 9:1)) in the presence of 20 vol % water were determined in a linear time-conversion region (Table 1).

TABLE 1 (CO)/μmol TON_(ReP) TOF_(ReP) (H₂)/μmol TON_(CoP) TOF_(CoP) Dye/TiO₂/ReP:CoP (10 h) (10 h) (10 h)h⁻¹ AQY/CO (10 h) (10 h) (10 h)h⁻¹ AQY/H₂ ReP:CoP 0.74 74 7.4 (9.2 ± 0.3) × 10⁻⁴ 4.19 47 4.7 (6.1 ± 0.2) × 10⁻³ (0.01:0.09 μmol) ReP:CoP 1.16 58 5.8 (1.0 ± 0.2) × 10⁻³ 3.37 42 4.2 (5.3 ± 0.2) × 10⁻³ (0.02:0.08 μmol) ReP:CoP 3.48 70 7.0 (2.6 ± 0.1) × 10⁻³ 3.09 62 6.2 (4.2 ± 0.2) × 10⁻³ (0.05:0.05 μmol) ReP:CoP 6.49 81 8.1 (3.7 ± 0.2) × 10⁻³ 2.82 141 14.1 (3.2 ± 0.2) × 10⁻³ (0.08:0.02 μmol) ReP:CoP 7.73 86 8.6 (4.6 ± 0.2) × 10⁻³ 2.21 221 22.4 (2.7 ± 0.3) × 10⁻³ (0.09:0.01 μmol) RuP/TiO₂/CoP — — — 5.66(4 h) 56.6(4 h) 44.0(1 h)h⁻¹ RuP/TiO₂/CoP — — — 0.24(4 h)  2.4(4 h)  0.6(1 h)h⁻¹ RuP/TiO₂/CoP — — — 1.23(4 h) 12.3(4 h) 10.3(1 h)h⁻¹ AQY (apparent quantum yield) = 2 × amount of H₂ or CO generated per unit time/number of incident photons per unit time

EXAMPLE 5 Confirmation of Persistency of Photocatalytic Activity

In order to confirm the persistency of photocatalytic activity, repetitive irradiation experiments were performed. No significant leveling-off tendency was observed in each cycle and the activity of syngas (CO and H₂) production was almost constant even with the extended catalytic cycles from 1st run to 4th run (FIG. 10). Overall the photocatalytic activities for CO and H₂ production in the inventive hybrid systems prepared are continuously increased up to 30 h with no appreciable leveling off tendency (FIG. 11). The initial gas compositions (H₂/CO ratio) are invariable during 10 hour reaction time. However, hydrogen evolution was a dominant feature in the extended reaction time (see FIG. 12 and Table 2).

TABLE 2 ReP CoP H₂/CO H₂/CO H₂/CO Entry System [μmol] [μmol] @5 hours @10 hours @20 hours 1 Dye/TiO₂/ReP:CoP(1:9) 0.01 0.09 5.3 5.3 14.5 2 Dye/TiO₂/ReP:CoP(2:8) 0.02 0.08 2.7 2.4 4.2 3 Dye/TiO₂/ReP:CoP(5:5) 0.05 0.05 0.8 0.8 1.3 4 Dye/TiO₂/ReP:CoP(8:2) 0.08 0.02 0.4 0.4 0.6 5 Dye/TiO₂/ReP:CoP(9:1) 0.09 0.01 0.3 0.3 0.4

EXAMPLE 6 Electron Transfer in Syngas Production

The photocatalytic reaction of syngas involves electron injection from excited-state Dye into TiO₂ as the initiation process (W. S. Han et al., Chem. Eur. J, 18:15368-81, 2012), competitive transfer of the injected electrons to the ReP and CoP catalyst sites through TiO₂, and the chemical processes proceeding on the ReP site (CO₂ reduction) and on the CoP site (H₂ evolution) under supply of electrons from TiO₂. This photocatalytic cycle for syngas production can be closed after the recovery of Dye by the reduction of Dye^(⋅+) with SED (FIG. 13). The ratio of CO and H₂ formed should primarily depend on the relative rates of electron supply from TiO₂ to the two catalysis sites, which would be determined by the relationship between the reduction potentials of ReP and CoP with respect to the conduction-band edge of TiO₂. The reduction potential of CoP is −0.88 V vs SCE (F. Lakadamyali et al., Chem. Eur. J., 18:15464-74, 2012), significantly less negative than that of ReP (RePE, −1.34 V vs SCE) (D. I. Won et al., J. Am. Chem. Soc., 137:13679-90, 2015) (FIG. 14) (FIG. 14).

EXAMPLE 7 Flat-Band Potentials (E_(fb)) on the Variation of Water Contents

The flat-band potential (E_(fb)) of TiO₂, which has been used as a practical measure of the conduction-band edge, is known to depend on solvents (G. Redmond et al., J. Phys. Chem., 97:1426-30, 1993). In a previous paper (D. I. Won et al., J. Am. Chem. Soc., 137:13679-90. 2015), the present inventors reported that E_(fb) positively shifts in the presence of water in DMF. FIG. 15 shows four different Mott-Schottky (MS) plots taken for TiO₂ nanoparticle films in the absence of water and in the presence of 3, 10, and 20 vol % water in acetonitrile. The increase of added water resulted in substantial positive shifts of E_(fb) from −1.93 V at 0% H₂O, to −1.74 V (3% H₂O), to −1.56 V (10% H₂O), and to −1.47 V (20% H₂O).

Provided that the E_(fb) values observed for the TiO₂ nanoparticle films can be applied to those of the TiO₂ hybrid particle dispersions in DMF, the electron transfer from TiO₂ to either ReP and CoP should be exergonic enough to proceed under the reaction conditions (A. Reynal et al., Ebergy Envrion. Sci., 6:3291-300, 2013; F. Lakadamyali et al., Chem. Eur. J., 18:15464-74, 2012; D. I. Won et al., J. Am. Chem. Soc., 137:13679-90, 2015). In fact, both CO and H₂ are generated in the presence of water (FIG. 7). It is of interest to note that the total amounts of CO and H₂ formed by irradiation of the TiO₂ hybrid catalyst with 0.05 μmol ReP: 0.05 μmol CoP in the presence of 3 to 20 vol % water are almost constant independently of the water contents while the H₂/CO ratios are variable with the water contents (FIG. 7). In this case, the total amounts of electrons utilized for the reductions of both CO₂ and H₂O would be constant but with different branch ratios of electron transfer depending on the water contents. The higher the water concentration, the faster the H₂-generation catalytic cycle should be completed to regenerate CoP. However, the ratios of the final products (CO and H₂) should be determined by complex factors, mainly by relative flows of both the first and second electrons to ReP and CoP and by efficiencies of the two-electron reduction catalytic cycles. The CO formation is dominant even in the presence of 10 vol % water (FIG. 7) where the concentration of H₂O (5.6 M) is much higher than that of CO₂ (˜0.2 M) (A. Gennaro et al., J. Electroanal. Chem., 289:203-15, 1990). A possible speculation is that electron supply from TiO₂ would more favorably occur to ReP than to CoP due to the different distances from the TiO₂ surface to the electron-accepting centers (the bpy ligand across the methylphosphonate spacer for ReP vs. Co^(III) across the pyridylphosphonate bridge for CoP) as well as due to the different configurational situations of the anchored molecules (double anchoring with the two phosphonate groups of ReP vs. single anchoring of the one phosphonate substituent of CoP). Alternatively, the catalytic cycle on the ReP site would more efficiently proceed than that on the CoP site in the presence of 10 vol % water, even though the CO formation on ReP involves more complex chemical processes than the H₂ evolution on CoP. In the presence of 20 vol % water, however, the formation of H₂ is more efficient than that of CO, probably due to the large amount of water that should accelerate the chemical processes for the H₂ generation. Also, this behaviour may be supported by the CO₂ concentration lessened with higher water content (consequently lowering the catalytic CO formation efficiency) since the solubility of CO₂ gas is generally much lower in water (˜0.034 M) than DMF solvent (˜0.2 M) (A. Gennaro et al., J. Electroanal. Chem., 289:203-15, 1990). The CO formation is sharply increased upon changing the anchoring amount of ReP from 0.01 μmol to 0.09 μmol, whereas the dependence of H₂ formation on the anchoring amount of CoP is not so remarkable (FIG. 8). In the presence of 20 vol % water, the catalytic cycle for H₂ generation would be efficient even with 0.01 μmol CoP enough to facilitate sufficient electron flow from TiO₂ to CoP in competition with the electron flow to 0.09 μmol ReP. This appears to be again true for the CO formation in cases where the anchoring amount of ReP is ≥0.05 μmol. The CO formation competes with or predominates over the H₂ generation even though the CO₂ concentration is much lower than the water concentration. The electron supply from TiO₂ to ReP and CoP might be dominated by a “seesaw mechanism” depending on the catalytic-cycle efficiencies under given reaction conditions. In addition, the poisoning of CoP catalyst by carbon monoxide should be considered as another reason of long-term instability of our photocatalytic system because the photocatalytic H₂ production by CoP proceeded in the presence of CO evolved from the co-catalyst ReP. In order to verify the negative effect of CO to the CoP complex during catalytic hydrogen production, the 78 μL CO gas (the amount of CO is equivalent to the amount of CO accumulated in the headspace (3 mL) of the reaction vessel with Dye/TiO₂/ReP:CoP (0.05 μmol:0.05 μmol) after 10 h of visible light illumination) was added to the reference condition (Dye/TiO₂/ReP (0.05 μmol):CoP (0.05 μmol)) before photoreaction; the resulting H₂ production activity were measured and compared with that without addition of CO. A slight reduction of H₂ production efficiency was observed in the photoreaction with addition of CO (FIG. 16), showing a negative influence of CO on catalytic H₂ generation (probably an inhibition of Co—H intermediate formation by CO coordination to the central Co metal site). However, overall the steady rise of H₂ production in the extended reaction period indicates that the CO poisoning effect is not a dominant feature in the inventive photocatalytic system probably due to the low solubility of CO in DMF solvent (FIG. 11).

While details of the present invention have been described above, it will be evident to those skilled in the art that such detailed descriptions are merely preferred embodiments and do not limit the scope of the present invention. Therefore, the true scope of the present invention should be defined by the appended claims and their equivalents. 

What is claimed is:
 1. A hybrid catalyst system comprising a hybrid catalyst comprising a semiconductor metal oxide, a dye, a rhenium (Re) catalyst, and a cobalt (Co) catalyst, wherein the dye, the rhenium (Re) catalyst, and the cobalt (Co) catalyst are grafted on the semiconductor metal oxide, wherein the rhenium (Re) catalyst is fac-[Re(4,4′-bis(diethoxyphosphoryl methyl)-2,2′-bipyridine)(CO)₃Cl], wherein the cobalt (Co) catalyst is Co^(lll)Cl(dimethylglyoximato)₂(pyridyl-4-phosphonic acid), wherein the molar ratio of rhenium (Re) catalyst/cobalt (Co) catalyst is from 9:1 to 1:9.
 2. The hybrid catalyst system according to claim 1, wherein the semiconductor metal oxide is TiO₂.
 3. The hybrid catalyst system according to claim 1, further comprising a sacrificial reagent as an electron donor.
 4. The hybrid catalyst system according to claim 1, further comprising a DMF/water mixture solvent.
 5. The hybrid catalyst system according to claim 4, wherein the water content is 20% by volume or less.
 6. The hybrid catalyst system according to claim 1, wherein the hybrid catalyst system produces hydrogen/carbon monoxide syngas.
 7. The hybrid catalyst system according to claim 6, wherein the hybrid catalyst system enables control over the ratio of hydrogen/carbon monoxide.
 8. The hybrid catalyst system according to claim 7, wherein the molar ratio of hydrogen/carbon monoxide is from 1:2 to 15:1.
 9. The hybrid catalyst system according to claim 6, wherein the hydrogen/carbon monoxide syngas is produced under visible light irradiation. 